The present invention relates in general to compositions for washing keratin materials, based on a detergent surfactant, a cationic galactomannan gum and an acrylic terpolymer, as well as to a washing process using these compositions.
Cationic guar gums are used in patent application EP 0 686 024 to improve the rheological properties of compositions containing crosslinked polymers. They are often used in shampoo compositions for the cosmetic qualities they impart to sensitized hair.
However, it has been found that these cationic galactomannan gums often have the drawback of reducing the cosmetic performance qualities of natural hair, in particular by making it more charged.
There is thus a need for a detergent cosmetic composition, in particular a shampoo, which gives acceptable cosmetic performance qualities on keratin materials, i.e. in particular the hair and the scalp and more particularly on natural hair.
The Applicant has discovered, surprisingly, that it is possible to formulate compositions for washing keratin materials, in particular shampoos, improving the cosmetic properties of keratin materials, and in particular of natural hair, by using in these compositions a detergent surfactant and a cationic galactomannan gum combined with a specific acrylic terpolymer, defined below. Specifically, it has been found that the use of the said acrylic terpolymer in the compositions of the present invention improves the cosmetic properties of keratin materials and in particular of natural hair, particularly by making wet natural hair feel softer and by giving dried natural hair greater lightness, softness, suppleness, smoothness, sheen and manageability.
A subject of the invention is thus compositions for washing keratin materials, essentially characterized in that they comprise, in a cosmetically acceptable medium:
i) at least one detergent surfactant;
ii) at least one cationic galactomannan gum; and
iii) at least one acrylic terpolymer consisting of:
from 5% to 80% by weight, preferably from 15% to 70% by weight and more preferably from 40% to 70% by weight, of an acrylate monomer (a) chosen from a C1-C6 alkyl acrylate and a C1-C6 alkyl methacrylate;
from 5% to 80% by weight, preferably from 10% to 70% by weight and more preferably from 20% to 60% by weight, of a monomer (b) chosen from a heterocyclic vinyl compound containing at least one nitrogen or sulphur atom, a (meth)acrylamide, a mono- or di(C1-C4)alkylamino(C1-C4)alkyl (meth)acrylate and a mono- or di(C1-C4) alkylamino (C1-C4) alkyl (meth) acrylamide;
from 0.1% to 30% by weight, preferably from 0.1% to 10% by weight, of a monomer (c) chosen from:
a urethane produced by reaction between a monoethylenic unsaturated isocyanate and a nonionic surfactant encompassing a block copolymer of 1,2-butylene oxide and of ethylene oxide containing a C1-C4 alkoxy end;
a copolymerizable ethylenic unsaturated surfactant monomer obtained by condensing a nonionic surfactant with an xcex1,xcex2-ethylenic unsaturated carboxylic acid or its anhydride;
a surfactant monomer chosen from reaction products such as urea of a monoethylenic unsaturated mono- isocyanate with a nonionic surfactant containing an amine function;
a (meth)allyl ether of formula CH2xe2x95x90CR1CH2OAmBnApR2 in which R1 denotes a hydrogen atom or a methyl group, A denotes a propylenoxy or butylenoxy group, B denotes ethylenoxy, n is equal to zero or denotes an integer less than or equal to 200 and preferably less than or equal to 100, m and p denote zero or an integer less than n and R2 is a hydrophobic group of at least 8 carbon atoms and preferably of 8 to 30 carbon atoms; and
a nonionic monomer such as urethane produced by reaction of a monohydric nonionic surfactant with a monoethylenic unsaturated isocyanate; the weight percentages of monomers being based on the total weight of the monomers constituting the terpolymer.
In the washing composition according to the invention, the acrylic terpolymer is present in a proportion of from 0.01% to 20% by weight of active material (A.M.), preferably 0.1% to 10% by weight, relative to the total weight of the composition.
Preferred acrylate monomers (a) in particular comprise C2-C6 alkyl acrylates. Ethyl acrylate is most particularly preferred.
Examples of preferred monomers (b) which may be mentioned are N,N-dimethylaminoethyl methacrylate (DMAEMA), N,N-diethylaminoethyl acrylate, N,N-diethyl-aminoethyl methacrylate, N-t-butylaminoethyl acrylate, N-t-butylaminoethyl methacrylate, N,N-dimethylamino-propylacrylamide, N,N-dimethylaminopropylmethacrylamide, N,N-diethylaminopropylacrylamide and N,N-diethylamino-propylmethacrylamide. N,N-Dimethylaminoethyl methacrylate is most particularly preferred.
The preferred monomers (c) are the copolymerizable ethylenic unsaturated surfactant monomers obtained by condensing a nonionic surfactant with an xcex1,xcex2-ethylenic unsaturated carboxylic acid or its anhydride, preferably C3-C4 mono- or dicarboxylic acids or their anhydrides and more particularly acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride and most particularly itaconic acid and itaconic anhydride.
The monomers (c) that are particularly preferred correspond to the copolymerizable ethylenic unsaturated surfactant monomers obtained by condensing a nonionic surfactant with itaconic acid. Among the nonionic surfactants which may be mentioned in particular are C10-C30 fatty alcohols alkoxylated with 2 to 100 mol and preferably from 5 to 50 mol of an alkylene oxide, such as, for example, polyethylene glycol ethers of C10-C30 fatty alcohols and more particularly the polyethylene glycol ethers of cetyl alcohol which are known as Ceteth in the CTFA dictionary, 7th edition, 1997.
Conventional methods for preparing these acrylic terpolymers are known to those skilled in the art. Such methods include solution polymerization, precipitation polymerization and emulsion polymerization, for example. Terpolymers in accordance with the invention and methods for preparing them are described in particular in patent applications EP-A-0 824 914 and EP-A-0 825 200.
Among these terpolymers, it is preferred in particular to use the  less than  less than Structure(copyright) Plus greater than  greater than  polymer sold by the company National Starch, which consists of acrylates, amino(meth)acrylates and C10-C30 alkyl itaconate, polyoxyethylenated with 20 mol of ethylene oxide polyoxyethylenated with 20 mol of ethylene oxide, in the form of an aqueous dispersion containing 20% A.M.
In addition to these monomers, the terpolymer can contain other monomers which allow the said terpolymer to be crosslinked. These monomers are used in relatively low proportions, of up to 2% by weight relative to the total weight of the monomers used to prepare the terpolymer. Such crosslinking monomers comprise aromatic monomers bearing several vinyl substituents, alicyclic monomers bearing several vinyl substituents, bifunctional esters of phthalic acid, bifunctional esters of methacrylic acid, multifunctional esters of acrylic acid, N-methylenebis-acrylamide and aliphatic monomers bearing several vinyl substituents such as dienes, trienes and tetraenes. Crosslinking monomers may be, in particular, divinylbenzenes, trivinylbenzenes, 1,2,4-trivinylcyclohexene, 1,5-hexadiene, 1,5,9-decatriene, 1,9-decadiene, 1,5-heptadiene, diallyl phthalates, ethylene glycol dimethacrylates, polyethylene glycol dimethacrylates, penta- and tetraacrylates, triallyl pentaerythritols, octaallyl sucroses, cycloparaffins, cycloolefins and N-methylenebisacrylamide.
The compositions in accordance with the invention also necessarily comprise a cationic galactomannan gum. The galactomannan gum is preferably a cationic guar gum.
The cationic galactomannan gums preferably have a cationic charge density of less than or equal to 1.5 meq/g and more particularly between 0.1 and 1 meq/g.
In general, for the purposes of the present invention, the expression  less than  less than cationic galactomannan gum greater than  greater than  means any galactomannan gum containing cationic groups and/or groups that can be ionized into cationic groups.
The preferred cationic groups are chosen from those comprising primary, secondary, tertiary and/or quaternary amine groups.
The cationic galactomannan gums used generally have a weight-average molecular mass of between 500 and 5xc3x97106 approximately, and preferably between 103 and 3xc3x97106 approximately.
The cationic galactomannan gums which can be used according to the present invention are, for example, gums comprising cationic tri(C1-C4)alkylammonium groups. Preferably, 2% to 30%, in numerical terms, of the hydroxyl functions in these gums bear trialkylammonium cationic groups.
Among these trialkylammonium groups which may be mentioned most particularly are trimethylammonium and triethylammonium groups.
Even more preferably, these groups represent from 5% to 20% by weight relative to the total weight of the modified galactomannan gum.
According to the invention, a guar gum comprising hydroxypropyl trimethylammonium groups, i.e. a guar gum modified, for example, with 2,3-epoxypropyltrimethylammonium chloride, is preferably used.
These galactomannan gums, in particular guar gums, modified with cationic groups, are products that are already known per se and are described, for example, in U.S. Pat. Nos. 3,589,578 and 4,031,307. Such products are moreover sold in particular under the trade names Jaguar C13S, Jaguar C15, Jaguar C17 and Jaguar C162 by the company Meyhall.
The galactomannan gums may be present in active material concentrations of between 0.005% and 10% by weight, preferably between 0.02% and 8% by weight and even more preferentially in proportions of between 0.05% and 5% by weight, relative to the total weight of the composition.
As mentioned previously, the compositions according to the invention contain at least one detergent surfactant, in particular chosen from anionic, amphoteric, nonionic and cationic surfactants with detergent properties, and mixtures thereof.
Among the anionic surfactants which may be mentioned are alkaline salts, ammonium salts, amine salts, amino alcohol salts and magnesium salts of the following compounds: alkyl sulphates, alkyl ether sulphates, alkylamido ether sulphates, alkylaryl polyether sulphates, monoglyceride sulphates; alkyl sulphonates, alkylamide sulphonates, alkylaryl sulphonates, olefin sulphonates, paraffin sulphonates; alkyl sulphosuccinates, alkyl ether sulphosuccinates, alkylamide sulphosuccinates; alkyl sulphosuccinamates; alkyl sulphoacetates; alkyl phosphates, alkyl ether phosphates; acyl sarcosinates, acyl isethionates, N-acyl taurates.
The alkyl or acyl radical in these various compounds generally consists of a carbon-based chain containing from 8 to 30 carbon atoms.
Among the anionic surfactants which may also be mentioned are fatty acid salts such as oleic, ricinoleic, palmitic and stearic acid salts; coconut oil acid or hydrogenated coconut oil acid; acyl lactylates, in which the acyl radical contains from 8 to 30 carbon atoms.
Surfactants considered as weakly anionic can also be used, such as polyoxyalkylenated carboxylic alkyl or alkylaryl ether acids or salts thereof, polyoxyalkylenated carboxylic alkylamido ether acids or salts thereof and alkyl D-galactosiduronic acids or salts thereof.
The nonionic surfactants are chosen more particularly from polyethoxylated, polypropoxylated or polyglycerolated fatty acids or alkylphenols or alcohols, with a fatty chain containing 8 to 30 carbon atoms, the number of ethylene oxide or propylene oxide groups being between 2 and 50 and the number of glycerol groups being between 2 and 30.
Mention may also be made of copolymers of ethylene oxide and propylene oxide; condensates of ethylene oxide and of propylene oxide with fatty alcohols; polyethoxylated fatty amides preferably containing 2 to 30 mol of ethylene oxide; polyglycerolated fatty amides preferably comprising 1 to 5 and in particular 1.5 to 4 glycerol groups; polyethoxylated fatty amines preferably containing 2 to 30 mol of ethylene oxide; oxyethylenated fatty acid esters of sorbitan with 2 to 30 mol of ethylene oxide; fatty acid esters of sucrose, fatty acid esters of polyethylene glycol, alkylpolyglycosides, carbamate or amide derivatives of N-alkylglucamines, aldobionamides, amine oxides such as alkylamine oxides or of N-acylamidopropylmorpholine.
The preferred amphoteric surfactants are secondary or tertiary aliphatic amine derivatives, in which the aliphatic radical is a linear or branched chain containing 8 to 22 carbon atoms and which contains at least one carboxylate, sulphonate, sulphate, phosphate or phosphonate water-solubilizing anionic group; (C8-C20)alkylbetaines, sulphobetaines, (C8-C20)alkylamido(C1-C6)alkylbetaines or (C8-C20)alkylamido(C1-C6) alkylsulphobetaines.
Among the amine derivatives which may be mentioned are the products sold under the name Miranol, gosuch as those described in patents U.S. Pat. Nos. 2,528,378 and 2,781,354 and classified in the CTFA dictionary, 7th edition, 1997, under the name Disodium Cocoamphodiacetate, Disodium Lauroamphodiacetate, Disodium Capryloamphodiacetate, Disodium Caproamphodiacetate, Disodium Cocoamphodipropionate, Disodium Lauroamphodipropionate, Disodium Caproamphodipropionate, Disodium Capryloamphodipropionate, Lauroamphodipropionate acid, Cocoamphodipropionate acid.
The cationic surfactants are chosen in particular from the salts of optionally polyoxyalkylenated primary, secondary or tertiary fatty amines; quaternary ammonium salts; imidazoline derivatives; or amine oxides of cationic nature.
The preferred quaternary ammonium salts are tetraalkylammonium halides (e.g. chlorides) such as, for example, dialkyldimethylammonium or alkyltrimethylammonium chlorides, in which the alkyl radical contains from about 12 to 22 carbon atoms, in particular behenyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride, benzyldimethylstearylammonium chloride or stearamidopropyldimethyl(myrietyl acetate)ammonium chloride sold under the name  less than  less than Cepharyl 70 greater than  greater than  by the company Van Dyk.
Diacyloxyethyldimethylammonium, diacyloxyethylhydroxyethylmethylammonium, monoacyloxyethyldihydroxyethylmethylammonium, triacyloxyethylmethylammonium, monoacyloxyethylhydroxyethyldimethylammonium salts (chlorides or methyl sulphate in particular) and mixtures thereof may also be used. The acyl radicals preferably contain 14 to 18 carbon atoms and are derived more particularly from a plant oil such as palm oil or sunflower oil.
The surfactants are used in the compositions in accordance with the invention in proportions that are sufficient to give the composition a detergent nature, generally in a proportion of at least 4% by weight, preferably between 5% and 50% by weight, relative to the total weight of the composition and in particular between 8% and 35%.
The compositions according to the invention have a pH generally of between 3 and 12 and more particularly between 4 and 8.
The cosmetically acceptable medium for the compositions consists either of water or of one or more solvents or of a mixture of water and at least one cosmetically acceptable solvent chosen from lower alcohols, alkylene glycols and polyol ethers.
In one preferred embodiment of the invention, the compositions according to the present invention contain modified or unmodified polyorganosiloxanes, i.e. polyorganosiloxane oils or polyorganosiloxane gums or resins, in their native form or in the form of solutions in organic solvents or alternatively in the form of emulsiong or microemuleions.
Among the polyorganosiloxanes which can be used in accordance with the present invention, mention may be made, in a non-limiting manner, of:
I. Volatile silicones: these have a boiling point of between 60xc2x0 C. and 260xc2x0 C. They are chosen from cyclic silicones containing from 3 to 7 and preferably 4 to 5 silicon atoms. Examples of these silicones are octamethylcyclotetrasiloxane sold under the name  less than  less than Volatile Silicone 7207 greater than  greater than  by Union Carbide or  less than  less than Silbione 70045 V2 greater than  greater than  by Rhxc3x4ne Poulenc, decamethylcyclopentasiloxane sold under the name  less than  less than Volatile Silicone 7158 greater than  greater than  by Union Carbide and  less than  less than Silbione 70045 V5 greater than  greater than  by Rhxc3x4ne Poulenc, as well as mixtures thereof. Mention is also made of cyclocopolymers of the dimethylsiloxane/methylalkylsiloxane type, such as  less than  less than Volatile Silicone FZ3109 greater than  greater than  sold by the company Union Carbide, which is a dimethylsiloxane/methyloctylsiloxane cyclocopolymer.
II. Non-volatile silicones: these consist mainly of:
(i) polyalkylsiloxanes; among the polyalkylsiloxanes which may mainly be mentioned are linear polydimethylsiloxanes containing trimethylsilyl end groups, such as, for example, and in a non-limiting manner, the  less than  less than Silbione greater than  greater than  oils of the 70047 series sold by Rhxc3x4ne Poulenc, the oil  less than  less than 47 V 500,000xe2x80x3 from Rhxc3x4ne-Poulenc, or certain  less than  less than Viscasil greater than  greater than  products from General Electric or  less than  less than Mirasil greater than  greater than  products from Rhxc3x4ne-Poulenc and linear polydimethylsiloxanes containing hydroxydimethylsilyl end groups, such as the oils of the series 48 V from Rhxc3x4ne-Poulenc;
(ii) polyarylsiloxanes;
(iii) polyalkylaryleiloxaneg; mention may be made of linear and branched polymethylphenylsiloxanes, polydimethylmethylphenylsiloxanes and polydimethyldiphenylsiloxanes, such as, for example, the oil  less than  less than Rhodorsil 763 greater than  greater than  from Rhxc3x4ne Poulenc;
(iv) silicone gums; these are polydiorganosiloxanes with a molecular mass of between 200,000 and 1,000,000, which are used alone or as a mixture in a solvent chosen from volatile silicones, polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, methylene chloride, pentane, dodecane, tridecane and tetradecane, or mixtures thereof; they have, for example, the following structures:
polydimethylsiloxane,
poly[(dimethylsiloxane)/(methylvinylsiloxane)],
poly[(dimethylsiloxane)/(diphenylsiloxane)],
poly[(dimethylsiloxane)/(phenylmethylsiloxane)],
poly[(dimethylsiloxane)/(diphenylsiloxane)/(methylvinylsiloxane)];
mention may also be made, by way of example, and in a non-limiting manner, of the following mixtures:
1) mixtures formed from a polydimethylsiloxane hydroxylated at the end of the chain (Dimethiconol according to the CTFA nomenclature) and from a cyclic polydimethylsiloxane (Cyclomethicone according to the CTFA nomenclature), such as the product  less than  less than Q2 1401 greater than  greater than  sold by the company Dow Corning;
2) mixtures formed from a polydimethylsiloxane gum with a cyclic silicone, such as the product  less than  less than SF 1214 Silicone Fluid greater than  greater than  from General Electric, which is an SE 30 gum of MW 500,000 dissolved in  less than  less than SF 1202 Silicone Fluid greater than  greater than  (decamethylcyclopentasiloxane);
3) mixtures of two PDMSs of different viscosity, in particular of a PDMS gum and of a PDMS oil, such as the products  less than  less than SF 1236 greater than  greater than  and  less than  less than CF 1241 greater than  greater than  from the company General Electric;
(v)silicone resins; preferably crosslinked siloxane systems containing R2SiO2/2, RSiO3/2 and SiO4/2 units in which R represents a hydrocarbon group containing 1 to 6 carbon atoms or a phenyl group. Among these resins, mention may be made of the product sold under the name  less than  less than Dow Corning 593 greater than  greater than ;
(vi) organomodified polyorganosiloxanes; i.e. silicones as defined above, comprising in their general structure one or more organofunctional groups directly linked to the siloxane chain or linked via a hydrocarbon-based radical; mention is made, for example, of silicones comprising:
a) polyethylenoxy and/or polypropylenoxy groups optionally comprising alkyl groups, such as the product known as dimethicone copolyol sold by the company Dow Corning under the name  less than  less than DC 1248 greater than  greater than  and the alkyl (C12) methicone copolyol sold by the company Dow Corning under the name  less than  less than Q2 5200 greater than  greater than ;
b) (per)fluoro groups, such as trifluoroalkyl groups, such as, for example, those sold by the company General Electric under the name  less than  less than FF.150 Fluorosilicone Fluid greater than  greater than ;
c) hydroxyacylamino groups, such as those described in European patent application EP-A-0 342 834 and in particular the silicone sold by the company Dow Corning under the name  less than  less than Q2-8413 greater than  greater than ;
d) thiol groups, such as in the silicones  less than  less than X 2-8360 greater than  greater than  from Dow Corning or  less than  less than GP 72A greater than  greater than  and  less than  less than GP 71 greater than  greater than  from Genesee;
e) substituted or unsubstituted amine groups, such as the products sold under the name GP 4 Silicone Fluid and GP 7100 by the company Genesee or the products sold under the names Q2 8220 and Dow Corning 929 or 939 by the company Dow Corning. The substituted amine groups are, in particular, C1-C4 aminoalkyl or amino (C1-C4)alkylamino(C1-C4) alkyl groups. The silicones known as amodimethicone and trimethylsilylamodimethicone according to the CTFA name (1997) are used more particularly;
f) carboxylate groups, such as the products described in European patent EP 186 507 from Chisso Corporation;
g) hydroxyl groups, such as the polyorganosiloxanes containing a hydroxyalkyl function, which are described in patent application FR-A-2 589 476;
h) alkoxy groups containing at least 12 carbon atoms, such as the product  less than  less than Silicone Copolymer F 755 greater than  greater than  from SWS Silicones;
i) acyloxyalkyl groups containing at least 12 carbon atoms, such as, for example, the polyorganosiloxanes described in patent application FR-A-2 641 185;
j) quaternary ammonium groups, such as in the product  less than  less than Abil K 3270 greater than  greater than  from the company Goldschmidt;
k) amphoteric or betaine groups, such as in the product sold by the company Goldschmidt under the name  less than  less than Abil B 9950 greater than  greater than ;
1) bisulphite groups, such as in the products sold by the company Goldschmidt under the names  less than  less than Abil S 201 greater than  greater than  and  less than  less than Abil S 255 greater than  greater than ;
(vii)block copolymers containing a linear polysiloxane-polyalkylene block as repeating unit; the preparation of such block copolymers used in the context of the present invention is described in European patent application EP 0 492 657 A1, the teaching of which is included in the present description by way of reference;
(viii) grafted silicone polymers, containing a non-silicone organic skeleton, consisting of a main organic chain formed from organic monomers containing no silicone, onto which is grafted, inside the said chain as well as, optionally, on at least one of its ends, at least one polysiloxane macromonomer; in particular those chosen more preferably from those described in U.S. Pat. Nos. 4,963,935, 4,728,571 and 4,972,037 and patent applications EP-A-0 412 704, EP-A-0 412 707, EP-A-0 640 105 and WO 95/00578, the teachings of which are included in their entirety into the present description by way of non-limiting references;
(ix) grafted silicone polymers, containing a polysiloxane skeleton grafted with non-silicone organic monomers, comprising a main polysiloxane chain onto which is grafted, within the said chain as well as, optionally, on at least one of its ends, at least one organic macromonomer containing no silicone; examples of such polymers, as well as the particular method for preparing them, are described in particular in patent applications EP-A-0 582 152, WO 93/23009 and WO 95/03776, the teachings of which are included in their entirety into the present description by way of non-limiting references;
(x) or mixtures thereof.
The polyorganosiloxanes preferably used according to the invention are non-volatile polyorganopolysiloxanes and preferably polydimethylsiloxane oils or gums and aminated, arylated or alkylarylated polydimethylsiloxanes.
The polyorganosiloxanes are used in the compositions of the invention in proportions of between 0.01% and 20% by weight and preferably between 0.1% and 10% by weight relative to the total weight of the composition.
In another preferred embodiment, the compositions of the invention also contain at least one cationic polymer other than galactomannan gums, chosen from all those already known per se, in particular those described in patent application EP-A-0 337 354 and in French patent applications FR-A-2 270 846, 2 383 660, 2 598 611, 2 470 596 and 2 519 863.
The cationic polymers used generally have a molecular mass of between 500 and 5 106 approximately and preferably between 103 and 3 106 approximately.
Among the cationic polymers which can be used in the context of the present invention, cellulose ether derivatives comprising quaternary ammonium groups and cyclopolymers of methyldiallylamine or of dimethyldiallylammonium are preferred.
These cationic polymers are used in the compositions of the invention in total proportions of between 0.001% and 20% by weight and preferably between 0.5% and 5% by weight, relative to the total weight of the composition.
The compositions according to the invention can furthermore also contain at least one adjuvant chosen from the adjuvants usually used in cosmetics, such as fragrances, preserving agents, sequestering agents, wetting agents, sugars, plant, animal, mineral or synthetic oils, amphoteric polymers, menthol, nicotinate derivatives, agents for preventing hair loss, antidandruff agents, foam stabilizers, propellants, dyes, screening agents, ceramides, vitamins or provitamins, acidifying or basifying agents or other well-known cosmetic adjuvants.
In one preferred embodiment of the invention, the compositions according to the invention are used as shampoos for washing the hair.
The process for washing keratin materials consists in applying a composition as defined above to wet or dry keratin materials in amounts that are effective to wash them, this application being followed by rinsing after an optional period of leaving the composition to stand on the keratin materials.